TW517107B - Improved clay-nylon polymer spinning properties - Google Patents

Abstract

When we have mixed Nylon monomer, water and clay, we put these mixtures into the reactor, then let mixtures to process the polymerization. We can synthesize Clay-Nylon polymer, and evaluate this polymer spinning properties and mechanical properties of these fibers. The spinning and mechanical properties was very poor when the clay amounts were larger than 2 weight %. We improved spinning and mechanical properties using dispersing agent to have treated clay in this invention. As to the clay amounts were 5 weight %, the spinning and mechanical properties was very good.

Description

517107 V. Description of the invention (1) The purpose of the present invention is to improve the spinnability of clay nylon polymer and the physical properties of the fibers obtained by spinning. The method used is to treat the clay with a dispersant, and then mix it with the nylon monomers caprolactam or hexamethylenediamine and adipic acid and water, and polymerize to obtain a clay nylon polymer, which can improve the spinning of the clay nylon polymer. And mechanical properties, especially when the clay content is greater than 2 weight percent. It can be found from the U.S. patent literature that a clay is treated with a dispersant and then polymerized with caprolactam to obtain a polymer, which is used to improve its heat resistance in the application of engineering plastics or composite materials, such as U.S. Patent No. 5, 747, 560, U.S. Patent No. 1 ^ 1 ^ 37,385, U.S. Patent No. 5,102,9 48, U.S. Patent No. 5,248,720, U.S. Patent No. 5,486,573, U.S. Patent No. No. 6, 121,361, U.S. Patent No. 6,117,931, U.S. Patent No. 6,103,817, U.S. Patent No. 5,973,053, U.S. Patent No. 5,656,7 09, etc. Yes. The main purpose of the present invention is to use an amino acid having 5 to 18 carbons as a dispersant. The treatment method is to dissolve the dispersant and clay in water, disperse the clay, and filter and dry to obtain powdery clay. Then, the clay treated with the dispersant is mixed with caprolactam or hexamethylenediamine and adipic acid and water, and then polymerized to synthesize clay nylon polymer and then spin into fibers. At this time, better spinnability and mechanical properties can be obtained. Fiber of nature. In the process of clay dispersion of the present invention, a strong acid (such as hydrochloric acid, sulfuric acid, or linoleic acid) is added to a mixture of clay, dispersant, and water, and the mixture is stirred at room temperature to 80 ° C, and then filtered and dried. , You can get the clay powder treated with dispersant, in which the amount of water is 1 to 100 times the weight of the clay,

517107 V. Description of the invention (2) The main purpose is to stir evenly. The used amount of the treated clay of the present invention is 0.01 to 10 weight percent (100 weight percent of clay nylon polymer), and the original clay needs to have 50 to 200 per 100 grams of clay. Milliquivalent exchangeable cations (sodium or calcium ions) 'dispersant is used in an amount! I to 100 g of water is used, and the strong acid is added in an amount of 0.05 to 5 equivalent percentages relative to all the exchangeable cations (sodium or calcium ions) in the untreated clay. The water used in the present invention is deionized water or distilled water. The nylon monomer used in the repolymerization process of the present invention may be a salt of nylon 6 monomer caprolactam or nylon 66 monomer hexamethylenediamine and adipic acid or adipic acid and adipic acid. In the polymerization process of the clay nylon mentioned in the present invention, some / xiaoguang agents (such as titanium dioxide), stabilizers (such as [rgan〇X lQl0 or phosphoric acid), and molecular weight control agents (such as acetic acid or phosphoric acid) can be added. A few examples are described below. The examples are merely general illustrations of the method of the present invention, and do not limit the scope of the present invention, and make a statement in this regard. Clay dispersion treatment: 200 grams of clay (montmorillonite; Yamagata, Japan

Products of Prefecture, whose exchangeable cation number is I (g milliequivalents per 100 grams of clay) are placed in a reaction tank, 6 liters of deionized water is added, and 102.4 grams of 12-aminolauric acid and 48.2 grams of concentrated phosphoric acid are added. After stirring at room temperature for 60 minutes, after filtering, drying at 100 ° C can obtain clay powder.

517107 V. Description of the invention (3) Example 1. Put the treated clay (see Table 1 for dosage) and 100 kg of caprolactam and 6 g of deionized water (relative to the weight of synthetic clay nylon polymer). In a 200-liter reaction tank, heat and stir uniformly, and the internal temperature rises to 260t: During the process, if the pressure is greater than 5kg / c rri, the pressure is discharged to 0kg / c m2, and the reaction is performed after 2 hours After depressurizing to Okg / crri, and then blowing with nitrogen for about 10 minutes, it began to cut and granulate to obtain clay nylon 6 polymer particles. The clay nylon 6 polymer particles are boiled in water until the weight is no longer reduced, and then dried, and then dissolved in concentrated sulfuric acid (96%) (concentration of 1 g / 1 00 ml of concentrated sulfuric acid), using a viscosity tube Cannon- 1 Measure its relative viscosity at 30 ° C (see Table 1 for results). After the above-mentioned boiled clay nylon 6 polymer particles are dried, they are spun out through an extruder. The spinning conditions are as follows: the polymer melting temperature is 27 ° C, the back pressure of the extruder is 110kg / c m2, and the temperature is cold. At room temperature, the cold wind speed is 0.8m / sec, and the take-up speed is 4,000 to 5000m / min. Each strand of the wire goes right 9 strands. See Table 24 for the physical properties after spinning. Comparative Example 1. Step In the same example, the clay used was not treated with 2-aminolauric acid and phosphoric acid. The results are shown in Table 1. 05 Comparative Example 1 Table 1 Silk Properties of Clay Nylon 6 Polymer after Spinning No. 01 0 2 〇3 〇4 Sample Source Example 1 Example 1 Example 1 Comparative Example j

Page 7 517107 V. Description of the invention (4) Clay content 0 2% (a) 5% (a) 5% (b) 2 ° / 〇 (b) Relative viscosity 2.5 5 2. 7 3. 1 3.2 2. 8 fineness 70d / 24f 70d / 24f 70d / 24f 70d / 24f 70d / 24f fiber strength 4. Og / d 4 · 2g / d 4.5g / d __ c L 8g / d (break point) slim elongation 38% 3 6 ° / 〇34% — 37% Fiber modulus 1 4g / d 20g / d 28g / d — 1 3g / d Coefficient of silk formation good Allison wire breakage is very good Broken wire rate 2 2 3 Many 3 (times / Set · hour) Note ... (1) Those with a mark in the clay content item indicate that the clay they used has been treated, and those with a b mark indicate that the clay has not been treated. (2) Good silk formation indicates good, and can indicate acceptable. It can be seen from the table above that the clay has been treated with a dispersant, and its synthetic clay nylon polymer has good silk-forming properties, and its fiber properties are also better (especially the fiber modulus is better). Example 2. The treated clay (the dosage is shown in Table 2), hexamethylene diamine and adipic acid (molar ratio of hexamethylene diamine and adipic acid; 100 kg in total) and 6 g of deionized water were placed in 20 In a 0 liter reaction tank, heat up and stir to 28 ° C.

Page 8 517107 Description of the invention During C2 f heating, when the pressure is greater than 5 kg / c m2, the pressure will be reduced to 0 kg / c = 2 ^ After the reaction time to 3 hours, the pressure will be reduced to 0 kg / c m2, and then Nitrogen was blown for about 10 minutes, and then feeding and granulation were started to obtain clay nylon 66 polymer particles. Then the clay nylon 6 6 particles were dried and dissolved in 96% concentrated sulfuric acid (concentration: 1 g / 100 ml). The viscosity of the tube was measured using the number Unnon—. After drying the synthetic clay nylon 6 6 polymer particles, the spinning conditions are as follows: the polymer melt temperature is 290 ° F, the back pressure of the extruder is 120 kg / cm2, and the cold air speed is room temperature. 0.9 m / sec., The take-up speed is 4000 to 50,000 m / min ·, and its physical properties after spinning are shown in Table 2. Comparative Example 2. The procedure was the same as in Example 2, except that the clay used was not treated with 1 2-aminolauric acid and phosphoric acid. Table 2. Physical properties of clay nylon 66 polymer after spinning No. 11 12 13 Sample source Example 2 Example 2 Comparative Example 2 Clay content 0 5 ° / 〇 (a) 5% (b) Relative viscosity 2.73. 4 3. 5 Fineness 70d / 24f 70d / 24f 70d / 24f Fiber strength 4 · lg / d 4 · 7g / d — (break point) Fiber elongation 36% 36% —

517107 V. Description of the invention (6) Fiber modulus 15g / d 29g / d — good filament formation, good broken wire, very strong broken rate 2 3 many (times / set · hour) Note: (1) clay content Those with a mark indicate that the clay they have used has been treated, and those with b mark indicate that the clay has not been treated. (2) Good silk formation indicates good, and can indicate acceptable. ^

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Claims (1)

517107 6. Scope of patent application 4. For example, the composition of improving the spinnability of clay nylon in item 1 of the scope of patent application, in which the strong acid of item (1) (PK = 0 to 2) can be hydrochloric acid, sulfuric acid and phosphoric acid. 5. For example, the improvement of the spinnability of clay nylon in item 1 of the scope of patent application, wherein the amount of water used for treating clay in item (1) is 5 to 50 times the weight of the clay to be treated. 6 · As described in item 1 of the scope of patent application, an improved spinnability composition of clay nylon, wherein the amount of treated clay in item (1) is 0.01 to 6 weight percent (relative to the weight of the synthesized clay nylon polymer) and nylon Clay nylon polymer is synthesized by monomer polymerization. Page 13 517107 ΊΠΤ 6. Scope of patent application 1 · An improved spinning property of clay nylon, which consists of (1) clay (50 to 200 milli-equivalent exchangeable cations per 100 grams of clay) via 5 to 1 8 A dispersant of amino carbonic acid (the amount of which is 1 to 100 grams of dispersant for water used to treat clay), a strong acid (PK value 0 to 2; the added amount is 0.05 to 5 equivalent percentages, relative to The total number of exchangeable cation equivalents in the untreated clay and the treated clay water (the amount of water is 1 to 100 times the weight of the clay to be treated) are placed in the reaction tank, and stirred at room temperature to 80 ° C. , Filter and dry, take the treated clay 0 · 0 1 to 10 weight percent (relative to the weight of the clay nylon polymer to be synthesized), and (2) nylon 6 monomer caprolactam or nylon 66 monomer hexamethylene Amine and adipic acid or salts of adipic acid and adipic acid, and (3) water for polymerization (the amount of which is 0.1 to 10 weight percent of the clay nylon polymer to be synthesized), at a temperature of 25 0 to 300 ° Clay nylon polymer is synthesized by reaction at C, and it is charged at 250 to 300 ° C. Machine extrusion spinning into fibers. 2. The composition of improving the spinnability of clay nylon, as described in item 1 of the scope of patent application, wherein 5 to 18 carbon amino acid dispersants in item (1) may be 5 to 12 carbon amino acids, such as 5 -Aminovaleric acid, 6-aminohexanoic acid, aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-amino group Lauric acid and so on. 3. The composition of improving the spinnability of clay nylon as described in item 1 of the scope of the patent application, where the amount of 5 to 18 carbon amino acid dispersant in item (1) is 5 to 9 per liter of treated clay water. 0 grams. Page 12